Path Function & Point

Function
Path Function
• Their magnitudes depend on the path followed during a process as
well as the end states. Work (W), heat (Q) are path functions.
Point Functions
• Point Function: They depend on the state only, and not on how a
system reaches that state. All properties are point functions.
 LAWS OF
THERMODYNAMICS
 Zeroth Law of Thermodynamics
• The zeroth law of thermodynamics states that if two systems, A and B,
are in thermal equilibrium with a third system, C, then A and B are in
thermal equilibrium with each other.
 Zeroth Law of Thermodynamics
• Consider three systems namely A, B and C. If the system A and B are
in thermal equilibrium separately and A and C are in thermal
equilibrium separately, then B and C should be in thermal equilibrium.
 Importance of Zeroth Law of
Thermodynamics
• The zeroth law is incredibly important as it allows us to define the
concept of a temperature scale.
• Temperature is considered to be the property which distinguishes
thermodynamics from the other sciences.
• It is by the property of temperature that we can make out the
difference between hot and cold body.
• Have you ever wondered why freezing point temperature of water is
zero degree Celsius and why its boiling point temperature is 100
degree Celsius?
• The Zeroth law of thermodynamics is the basis for measurement of
temperature and setting its scale.
 Importance of Zeroth Law of
Thermodynamics
• To measure the temperature of the body some reference body is
required and some characteristics of the body that change with
temperature. The changes in the characteristics of the body with
temperature can be taken as an indication of change in temperature.
• The selected characteristic that changes with temperature is called
thermometric property and the body which is used as the reference is
called as thermometer.
• You all know the ordinary thermometer that consists of mercury in a
capillary tube. In this case mercury is the reference body.
 Importance of Zeroth Law of
Thermodynamics
• When we keep the thermometer in contact with a body whose
temperature is to be measured the body (Say system B) and the
Capillary tube(Say system A) will become in thermal equilibrium with
each other, then the Capillary tube (System A) and mercury(Say
system C) inside it will become in thermal equilibrium and by zeroth
law of thermodynamics the body (system A) and mercury (System C)
will be in equilibrium. That is the body and the mercury will attain
same temperature. As the temperature of mercury changes, its
volume also changes, and by measuring the volume change of
mercury the temperature of body can be easily identified.
 Importance of Zeroth Law of
Thermodynamics
• Now, let’s come back to our freezing and boiling point temperatures
of water. To mark zero and 100 degree Celsius temperatures and
other temperatures between this range the head tip of thermometer
that contains mercury is dipped in water. As the temperature of water
changes the level of mercury within capillary goes up or down.
Initially the temperature of water is reduced so the level of mercury in
capillary also goes down. The point at which water gets converted to
ice is called freezing point temperature of water and the level of
mercury obtained at this temperature is marked as zero degree
Celsius.
 Importance of Zeroth Law of
Thermodynamics
• Then the temperature of water is increased gradually and at some
particular level it starts boiling, this temperature is called as boiling
point temperature of water and the level of mercury at this
temperature is marked as 100 degree Celsius. Thereafter, all the other
temperatures are marked at equal distance between 0 and 100
degree Celsius. This is how zero degree Celsius as freezing point, 100
Celsius as boiling point, and other temperatures are set.
 First Law of Thermodynamics
• The laws of thermodynamics are not like theorems in mathematics,
which can be proved by deduction or inductive logic. They are based
on experimental facts. So far, no experimental evidence is available to
cast any doubt on the correctness of these laws. The first law of
thermodynamics deals with the conservation of energy of a system
which undergoes a change of state as a result of work and heat
interactions.
First Law of Thermodynamics
 First Law of Thermodynamics
• A series of experiments carried out by Joule between 1843 and 1848 form the
basis for the first law of thermodynamics. Of the several experiments carried out
by Joule, the paddle wheel experiment is considered as the classic. In Joul’s
experiment, a known amount of water was taken in a rigid and insulated vessel.
The vessel was provided with a paddle wheel driven by a mass m. Work was
done on the system (water in the vessel) by lowering the mass m, through a
distance (Z1-Z2). The work done on the system was computed in terms of the
change in potential energy of mass m. The thermometer immersed in the water
was used to determine the change in the state of the system. The temperature
of water was found to increase after work had been performed on the system.
Once the system had come to “rest”, it was brought in to contact with a water
bath and the system was allowed to come to the initial state. The amount of
energy transferred as heat from the system to the bath was estimated in terms
of the temperature rise of the bath. In this particular experiment, the system
underwent a series of processes and was restored to the initial state. In other
words, it went through a cyclic change.
 First Law of Thermodynamics
• A s a result of these experiments, Joule found that the net work done
on the system was always proportional to the net energy removed
from the system as heat, irrespective of the type of work interaction,
the rate at which work was done on the system, and the method
employed for transferring the energy in the form of work in to
thermal energy.
• Net heat transfer = Net work transfer
 First law of thermodynamics

• The first law of thermodynamics can be

stated as: whenever a system undergoes a
cyclic change, however complex the cycle
may be, the algebraic sum of the work
transfers is equal to the algebraic sum of
energy transfers as heat.
• It is inconvenient to specify every time whether work is done by the
system or on the system, energy is transferred as heat from the
system or to the system. Hence we adopt the following sign
convention for work and heat. Work done by a system on its
surroundings is assigned a positive sign and work done by the
surroundings on the system is assigned a negative sign. The energy
transfer as heat from surroundings to system is assigned a positive
sign, and energy as heat from system to its surroundings is assigned a
negative sign.
 Significance of First law of
thermodynamics
• The first law of thermodynamics is an expression of the principle of
conservation of energy. The first law expresses that energy can be
transformed (i.e. changed from one form to another), but cannot be
created or destroyed.
Limitations of First law of Thermodynamics

• The first law of thermodynamics is a law of conservation of energy

only. It does not specify the direction of the process.
• All spontaneous process proceed in one direction only. The first law of
thermodynamics does not deny the feasibility of a spontaneous
process reversing itself.
 Perpetual motion machine of first
kind (PMM1)
• Perpetual motion machine of first kind does not exist because such machines
violate the first law of thermodynamics.
• Perpetual motion machine of first kind (PMM1) is a cyclically operating device which
delivers work without requiring any interaction with the surroundings.
• Since the device does not interact with the surroundings and hence , which means
no work is done.
• Such machines is said to produce the energy by itself and as we know that
according to the law of energy conservation, energy could not be created or
destroyed but could be converted from one form of energy to other form of energy.
• Therefore, a machine that does not follow the first law of thermodynamics or law of
conservation of energy could be termed as perpetual motion machine of first kind
i.e. PMM1
Perpetual motion machine of first
kind (PMM1)
 Second Law of thermodynamics

• There are two statements of the second law of thermodynamics.

• (a)Kelvin Plank Statement
• It is impossible for a heat engine to produce net work in a complete cycle
if it exchanges heat only with bodies at a single fixed temperature.
• The Kelvin plank statement of second law of thermodynamics tells the
impossibility of PMM II. Perpetual motion machines of second kind
(PMM II) are those which does not obey second law of thermodynamics.
They absorb energy as heat from a single thermal reservoir and delivers
equivalent amount of work continuously. They do not exist.
 Second Law of thermodynamics

• There are two statements of the second law of thermodynamics.

•
 Significance of Second Law of
Thermodynamics
• The Clausius statement of second law of thermodynamics tells that
spontaneous process cannot proceed in the reverse direction.
• The second law of thermodynamics distinguishes between reversible
and irreversible process.
 Reversible and Irreversible Process
• A reversible process is one which is performed in such a way that at
the conclusion of the process, both the system and surrounding may
be restored to their initial state, without producing any changes in the
rest of the universe.
• The process which can occur in only one direction is called irreversible
process. The characteristics of irreversible process are
• An irreversible process can be carried out in only one direction.
• During an irreversible process, the system is not in equilibrium
• An irreversible process cannot be reversed without causing
permanent changes in the surroundings.
 Reversible and Irreversible Process
Examples of Reversible Process Examples of Irriversible Process

1. Motion without friction Motion with friction

2. Expansion or compression with no Expansion or compression with finite
pressure difference between the pressure difference
system and surroundings.

3. Energy transfer as heat with no Energy transfer as heat with finite

temperature difference across the temperature difference across the
system boundary system boundary

4. Mixing of matter at different ststes

5. Mixing of different gases
6. Spontaneous Process
 Sources of Power
• There are nine major areas of energy resources. They fall into two
categories: nonrenewable and renewable. Nonrenewable energy
resources, like coal, nuclear, oil, and natural gas, are available in
limited supplies. This is usually due to the long time it takes for them
to be replenished. Renewable resources are replenished naturally and
over relatively short periods of time. The five major renewable energy
resources are solar, wind, water (hydro), biomass, and geothermal.
 Sources of Power
Fuel
• Coal, oil, natural gas (or gas generated from landfills), wood fires, and
hydrogen fuel cell technology are all examples of fuels,, usually being
combusted to generate heat energy. Fuels may be either renewable
(like wood or bio-fuel generated from products such as corn) or
nonrenewable (like coal or oil). Fuels generally create waste
byproducts, some of which can be harmful pollutants.
 Sources of Power
Geothermal:
The Earth generates a lot of heat while going about its normal business,
in the form of subterranean steam and magma among others. The
geothermal energy generated within the Earth's crust can be harnessed
and transformed into other forms of energy, such as electricity.
 Sources of Power
Geothermal:
The Earth generates a lot of heat while going about its normal business,
in the form of subterranean steam and magma among others. The
geothermal energy generated within the Earth's crust can be harnessed
and transformed into other forms of energy, such as electricity.
 Sources of Power
Hydropower:
The use of hydropower involves using the kinetic motion in water as it
flows downstream, part of the normal water cycle of the Earth, to
generate other forms of energy, most notably electricity.
Dams use this property as a means of generating electricity. This form
of hydropower is called hydroelectricity. Waterwheels were an ancient
technology which also made use of this concept to generate kinetic
energy to run equipment, such as a grain mill, though it was not until
the creation of modern water turbines that the principle of
electromagnetic induction was used to generate electricity.
 Sources of Power
Hydropower:
The use of hydropower involves using the kinetic motion in water as it flows
downstream, part of the normal water cycle of the Earth, to generate other
forms of energy, most notably electricity.
Dams use this property as a means of generating electricity. This form of
hydropower is called hydroelectricity. Waterwheels were an ancient technology
which also made use of this concept to generate kinetic energy to run
equipment, such as a grain mill, though it was not until the creation of modern
water turbines that the principle of electromagnetic induction was used to
generate electricity.
 Sources of Power
Solar:
The sun is the single most significant source of energy to the planet
Earth, and any energy that it provides which isn't used to help plants
grow or to heat the Earth is basically lost. Solar power can be used with
solarvoltaic power cells to generate electricity. Certain regions of the
world receive more direct sunlight than others, so solar energy is not
uniformly practical for all areas.
 Sources of Power
• Wind:
• Modern windmills can transfer the kinetic energy of the air flowing
through them into other forms of energy, such as electricity. There are
some environmental concerns with using wind energy, because the
windmills often injure birds who may be passing through the region.
 Sources of Power
• Nuclear:
Certain elements undergo radioactive decay. Harnessing this nuclear
energy and transforming it into electricity is one way to generate
substantial power. Nuclear power is controversial because the material
used can be dangerous and resultant waste products are toxic. Accidents
that take place at nuclear power plants, such as Chernobyl, are
devastating to local populations and environments. Still, many nations
have adopted nuclear power as a significant energy alternative.
As opposed to nuclear fission, where particles decay into smaller
particles, scientists are continuing to study feasible ways of harnessing
nuclear fusion for power production.
 Sources of Power
• Biomass:
• Biomass is not really a separate type of energy, so much as a specific
type of fuel. It is generated from organic waste products, such as
cornhusks, sewage, and grass clippings. This material contains residual
energy, which can be released by burning it in biomass power plants.
Since these waste products always exist, it is considered a renewable
resource.
 Sources of Power
• Ocean Thermal Energy Conversion
• Oceans cover 70 percent of the
Earth, and water is a natural solar
energy collector. OTEC, or ocean
thermal energy conversion, aims to
exploit this fact and use the
temperature differences between
surface water heated by the sun and
water in the ocean's chilly depths to
generate electricity.
 Sources of Power
• Fuel Cells
• They can generate electricity using
only hydrogen and oxygen and are
pollution free. An automobile
running on hydrogen fuel cells would
not only be more efficient than one
powered by an internal combustion
engine, its only emission would be
water.